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Патент USA US3031451

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United States Patent ()?ice
3,031,441
Patented Apr. 24, 1962
1
2
3031441
washed with an ethanolic solution of hydrochloric acid,
then with water and ?nally with ethanol.
PROCESS FOR PREPARING POLYBUTADIENES
Albert Verheyden, 15 Kleine Geutstraat, St. Denis
Westrem, Belgium, and Paul Ochsner, 10 Rue de la
Dole, Geneva, Switzerland
No Drawing. Fiied May 26, 1958, Ser. No. 737,513
Claims priority, application Belgium June 6, 1957
15 Claims.‘ (Cl. 260-—94.3)
By polymerization of diole?nes, polymers are obtained 10
To avoid the degradation of the polymer during its
drying, an anti-oxidant such as betaphenylnaphthylamine
is added to the ethanol.
The polymers prepared according to our invention ‘are
non-sticky solids whose greater part is insoluble in
boiling diethyl ether. Infra-red spectra of these polymers
show that they contain at least 70% of 1,2-addition units‘.
The said polymers are useful for making various arti
lysts used. The Belgian Patent 549,554 ?led on July 14,
1956 by Montecatini discloses the polymerization of bu—
cles using compression or injection moulding, extrustion
in sheets, tubes or threads, wire-drawing by melting or
starting from solutions.
tadiene with speci?c catalysts, the polymers prepared
The following examples disclose several applications
whose structure varies with the compositions of the cata
having 1,2-additio-n uni-ts. These catalysts are obtained 15 of the invention‘, but they do not limit it in any way.
by reacting an o-rganometallic compound of a metal of
Example 1
the groups I, II or HI of the periodic classi?cation of the
elements with an oxyderivative of a transition metal of
the groups IV, V or VI of the same classi?cation.
_
100 g. of pure 1,3-butadiene are liqui?ecl at -4(}‘’ C.‘
in a glass container. One adds thereto by stirring a
The present invention is relating to the polymerization 20 catalyst prepared by reacting 25 millimoles of amyl
sodium and 3 millimoles of diethylzinc with 10 millimoles
of 1,3-butadiene in the form of non—sticky solids with ‘a
of anhydrous ferric chloride in 60 ml. of pentane. The
high ratio of 1,2-addition units wherein new catalysts are
mixture is stirred for 1 hour at —-'40° C. Then the tem
used. The new catalysts are obtained by reacting an
perature rises slowly to evaporate the excess of the
organosodiurn compound with a derivative of a metal of
the groups VII and VIII of the periodic classi?cation of 25 monomer. After 24 hours, the reaction product is treated
the elements. The mechanical properties of the poly
mers prepared are improved by addition of small amounts
of an organozinc or an organocadrnium compound.
The organosodium compound is generally amylsodium.
The organosodium compounds are prepared by known.
methods and, for instance, byv reacting ?nely divided ,
with‘ ethanol. The ?ltered polymer is washed with an
ethanolic solution of hydrochloric acid and then with
water to dissolve the formed salts. The last washing is
effected with an ethanolic solution of beta-phenylnaphthyl- '
amine. Finally, the polymer is dried at room tempera '
ture. 45 g. of a white solid are obtained. The 1,2
addition units ratio is of 73%. 56% of they polymer
are insoluble in boiling ether.
The organozinc and organocadmium compounds are
obtained by known methods.
Example 2
The derivatives of the metals of the groups VII and 35
l0
millimoles
of
anhydrous
ferric chloride are added
VIII used for the preparation of the catalysts are for in
to a mixture of 25 millimoles of amylsodium in 150 ml.
stance anhydrous chlorides of manganese, iron, nickel.
of pentane. The catalyst so prepared is transferred in an
and cobalt. Oxyorganoderivatives may also be used such
metallic sodium and alkyl chloride.
iron pressure-resisting tube ?tted with a manometer and
as nickel and cobalt acetylacetonates. We have found
that iron acetylacetonate maynot give polymers having 40 having a capacity of 280 ml. On the cover is placed a
pressure reducing valve. The tube is placed in a vertical
position and the base is connected with a cylinder'of l,3~
butadiene. A ?ow of gaseous 1,3-butadiene is passed
1 mole of a compound of a metal of the groups VII and 45 through the tube to remove the air remaining in it.
Then the pressure reducing valve is shut down and tuna
VIII, it is necessary to take from 0.5 to 5.0 moles of the
diene is introduced until the pentane is saturated under a
organosodium compound and from 0.05 to 1.0 mole of
pressure of 1.5 kg. by square centimeter. This pressure
an o-rgano-zinc or organocadrnium compound. We have
is maintained during 20 hours at a temperature of 20° C.
found that the optimal proportions are, for 1 mole of a
compound of a metal of the groups VII and VIII, from 50 The excess of gas is driven off by the upper part of the
tube.' The reaction product contained in the tube is
1 to 3 moles of an organosodium compound and from
washed with ethanol to decompose the catalyst. The
0.1 to 0.4 mole of an organozinc or organocadmium
puri?cation of the polymer is made as described in Ex
compound.
ample l. 30 g. of a solid product with 74% of 1,2-addi
The polymerization of butadiene occurs in the resence
tion units‘ are obtained. 36% of the polymer are insolu
of a solvent and preferably in the presence of an aliphatic
ble in boiling ether.
hydrocarbon such as pentane. When liquid butadiene is
Example 3
polymerized, the quantity of solvent may be reduced to
the minimum volume necessary for handling the catalyst.
A catalyst is prepared by reacting 20 millirnoles of
good properties. -
'
.'
.
The proportions of the compounds used for the prepa
‘ration of the catalysts vary in the following limits. For
The polymerization temperature is comprised between
ferric chloride with a mixture of 25 rnillirnoles of amyl
—40 and +40° C. and preferably of ‘about 20° C. The 60 sodium and 1.15 millirnoles of diethylcadmium. The
pressure is always lower than 5 atmospheres and’ prefer
conditions of the polymerization are the same as in Ex
ably of about 1.5 atmospheres. When the polymerization
occurs at atmospheric pressure, the temperature must be
maintained under the boiling point of the 1,3-buta-dieue.
ample 2. After'washings, ‘9 g. of a polymer are obtained
whose 79% are insoluble in boiling ether and with 74%
of 1,2-addition units.
Example 4
The polymerization is completed after from 4 to 24 65
hours and generally after 20 hours.
A catalyst is prepared by reacting '10 millimoles of
The catalyst is introduced in the reaction medium be
ferric chloride with a mixture of 25 millimoles of amyl
fore or during the polymerization. When a solvent is
sodium and 1.2 millimoles of diethylzinc. The conditions
used, the catalyst must be present before the butadiene
of the polymerization are the same as in Example 2.
70 After washings, 13 g. of a polymer are obtained whose
is added.
_
When the polymerization is completed, the catalyst is
85% are insoluble in boiling ether and with 72% of 1,2
decomposed by an aliphatic alcohol. The polymer is
addition
units.
7
'
.
s,os1,44.1
3
of the reaction product of (a) from 1 to 3 moles of amyl
sodium, (b) 1 mole of a compound selected from the
group consisting of manganese chloride, iron chloride,
Example 5
A catalyst is prepared by reacting 10 millimoles of
nickel acetylacetonate with a mixture of 25 millimoles of
nickel chloride, cobalt chloride, nickel acetylacetonate
amylsodium and 3.16 millimoles of diethylcadmium. The
and cobalt acetylacetonate, and (c) from 0.1 to 0.4 mole
of a member selected from the group consisting of di
conditions of the polymerization are the same as in Ex
ample 2. After washings, 15 g. of ‘a polymer are obtained
whose 55% are insoluble in boiling ether and with 72%
ethylcadmiunr and diethylzinc, whereby solid non-sticky
polybutadiene having a ratio of 1,2-addition units in ex
cess of 70% is formed.
- of 1,2-addition units.
Example 6
10
A catalyst is prepared by reacting 10 milllmoles of an- .
hydrous cobalt chloride with 25 millimoles of amylso
dium. The conditions of the polymerization are the same
as in Example 2. After: washings, 11 g. of a polymer are
obtained whose 36% are insoluble in boiling ether and
5. A catalyst which consists essentially of the reaction
product of (n) from 0.5 to 5 molecular equivalents of
amyl sodium and (b) 1 molecular equivalent of a com—
pound selected from the group consisting of manganese
chloride, iron chloride, nickel chloride, cobalt chloride,
nickel acetylacetonate and cobalt acetylacetonate.
6. A catalyst which consists essentially of the reaction
product of (a) from 1 to 3 molecular equivalents of amyl
with 73% of 1,2-addition units.
When the catalyst is prepared from 10 millimoles of
sodium, (12) 1 molecular equivalent of a compound se
anhydrous cobalt chloride, 3.16 millimoles of diethyl
lected from the group consisting of manganese chloride,
cadmium and 25 millimoles of amylsodium, the propor
20
iron
chloride, nickel chloride, cobalt chloride, nickel ace~
tion of the polymer insoluble in boiling ether is of 83%.
tylacetonate and cobalt acetylacetonate and (c) from 0.1
Example 7
to 0.4 molecular equivalent of a member selected from
A catalyst is prepared by reacting 10 millimoles of an
hydrous manganese dichloride (MnClz) with 25 milli
moles of amylsodium' The conditions of the polymeriza
the group consisting of diethylcadmium and diethylzinc.
prising contacting said butadiene with catalyst in the
tion are the same as in Example 2.
presence of an aliphatic hydrocarbon as solvent at a tem
7. The catalytic polymerization of 1,3-butadiene com
10 g. of a polymer
perature between —40° and +40° C. and at the pressure
of at most 5 atmospheres, said catalyst consisting essen
are obtained whose 33% are insoluble in boiling ether and
with 75% of 1,2-addition units.
When the catalyst is prepared from 10 millimoles of
anhydrous manganese dichloride, 3.16 millirnoles of di
ethylcadmium and 25 millimoles of amylsodium, the pro
portion of the polymer insoluble in boiling either is of
.70%.
tially of the reaction product of (a) 25 molecular equiv
alents of amyl sodium, ([2) 10 molecular equivalents of
anhydrous ferric chloride and (c) 3 molecular equivalents
of diethylzjnc, whereby solid non-sticky polybutadiene
having a ratio of 1,2-addition units in excess of 70% is
I
formed.
We claim:
1. Process for preparing polybutadiene in the form of 35
a non-sticky solid with a 1,2-addition units ratio greater
presence of an aliphatic hydrocarbon as solvent at a
than 70% which comprises contacting 1,3-butadiene
with a catalyst which consists essentially of the product
temperature between —40° and +40° C. and at a pres
sure of at most 5 atmospheres, said catalyst consisting es
from 0.5 to 5 moles of amylsodiurn and from 1 mole of a
sentially of the reaction product of (a) 25 molecular
equivalents of amyl sodium and (b) 10 molecular equiv
alents of anhydrous ferric chloride, whereby solid non
sticky polybutadiene having a ratio of 1,2-addition units
compound selected from the group consisting of manga
nese, iron, nickel and cobalt chlorides and nickel and co
balt acetylacetonates, said contacting being carried out at
a temperature between —40° and +40° C., under a pres
sure not exceeding 5 atmospheres and in the presence of
an aliphatic hydrocarbon as solvent.
'
in excess of 70% is formed.._
45
2. Process for preparing polybutadiene in the form of
9. The catalytic polymerization of 1,3-butadiene com
prising contacting said hutadiene with a catalyst in the
presence of an aliphatic hydrocarbon as solvent ata tem
perature between —-40° and +40° C. and at a pressure
a non-sticky solid with a 1,2-addition unit ratio greater
than 70% which comprises contacting 1,3-butadiene with
a catalyst which consists essentially of the product from
0.5 to 5 moles of amylsodium, from 1 mole of a com
'
8. The catalytic polymerization of 1,3-butadiene com
prising contacting said butadiene with a catalyst in the
50
pound selected from the group consisting of manganese,
iron, nickel and cobalt chlorides, nickel acetylacetonate
of at most 5 atmospheres, said catalyst consisting essen
tially of the reaction product of (a) 25 molecular equiv
alents of amyl sodium, ([2) 20 molecular equivalents of
ferric chloride and (c) 1.15 molecular equivalents of di
and cobalt acetylacetone and from 0.05 to 1 mole of a
ethylcadrnium, whereby solid non-sticky polybutadiene
compound selected from the group consisting of diethyl
cadmium and diethylzinc, said contacting being carried
having a ratio of 1,2-addition units in excess of 70% is
formed.
out at a temperature between —40° and +40° C., under
a pressure not exceeding 5 atmospheres and in the pres
ence of an aliphatic hydrocarbon as solvent.
3. The ‘catalytic polymerization of 1,3-butadiene com
prising contacting said butadiene with a catalyst in the 60
10. The catalytic polymerization of, 1,3-butadiene
comprising contacting said butadiene with a catalyst in
the presence of an aliphatic hydrocarbon as solvent at a
temperature between —40° and +40° C. and at a pres
sure of at most 5 atmospheres, said catalyst consisting
at most 5 atmospheres, said catalyst consisting essentially
essentially of the reaction product of (a) 25 molecular
equivalents of amyl sodium, (b) 10 molecular equivalents
of ferric chloride and (c) 1.2 molecular equivalents of
sticky polybutadiene having a ratio of 1,2-addition units
presence of an aliphatic hydrocarbon as solvent at a tem
presence of an aliphatic hydrocarbon as solvent at a tem
perature between -——40° and +40° C. and at a pressure of
diethylzinc, whereby solid non-sticky polybutadiene hav
of the reaction product of (a) from 0.5 to 5 moles of
amylsodium, and (b) 1 mole of a compound selected 65 ing a ratio of 1,2-addition units in excess of 70% is
formed.
from the group consisting of manganese chloride, iron
11. The catalytic polymerization of 1,3-butadiene com
chloride, nickel chloride, cobalt chloride, nickel acetyl
prising contacting said butadiene with a catalyst in the
acetonate and cobalt acetylacetonate, whereby solid non
70 perature between ——40°. and +40° C. and at a pressure
of at most 5 atmospheres, said catalyst consisting essen
4. The catalytic polymerization of 1,3-butadiene com~
tially of the reaction product of (a) 25 molecular equiv
prising contacting said butadiene with a catalyst in the
in excess of 70% is formed.
alents of amyl. sodium, (b) 10 molecular equivalents of
nickel acetylacetonate and (c) 3.16 molecular equiv
about 1.5 atmospheres, said catalyst consisting essentially 75 lents of diethylcadmium, whereby solid non-sticky poly
presence of an aliphatic hydrocarbon as solvent at a tem
perature between l—40° and +40° C(and at a pressure of
a,
butadiene having a ratio of 1,2-addition units in excess
of 70% is formed.
12. The catalytic polymerization of 1,3-butadiene com
prising contacting said butadiene with a catalyst in the
presence of an aliphatic hydrocarbon as solvent “at a tem
perature between ——40° and +40° C. and at a pressure
of at most 5 atmospheres, said catalyst consisting essen
atially of the reaction product of (a) 25 molecular equiv
alents of amyl sodium and (b) 10 molecular equivalents
of anhydrous manganese dichloride (MnClZ), whereby
solid non-sticky polybutadiene having a ratio of 1,2-addi
tion units in excess of 70% is formed.
15. The catalytic polymerization of 1,3-butadiene com
prising contacting said butadiene with a catalyst in the
tialiy of the reaction product of (a) 25 molecular equiv
alents of aniyl sodium and (b) 10 molecular equivalents
of anhydrous cobalt chloride, whereby solid non-sticky
presence of an aliphatic hydrocarbon as solvent at a tem
polybutadiene having a ratio of 1,2-addition units in ex
tially of the reaction product of (a) 25 molecular equiv
alents of amyl sodium, (5) 10 molecular equivalents of
anhydrous manganese dichloride and (c) 3.16 molecular
cess of 70% is formed.
13. The catalytic polymerization of 1,3-butadiene corn
prising contacting said butadiene with a catalyst in the
perature between ~40” and +4il° C. and at a pressure
of at most 5 atmospheres, said catalyst consisting essen
equivalents of diethylcadmium, whereby solid non-sticky
presence of an aliphatic hydrocarbon as solvent at a tem 15 polybutadiene having a ratio of 1,2-addition units in ex
cess- of 70% is formed.
perature between ~40” and +40° C. and at a pressure
of at most 5 atmospheres, said catalyst consisting essen
References Cited in the ?le of this patent
tially of the reaction product of (a) 25 molecular equiv
alents of amyl sodium, (b) to molecular equivalents of
anhydrous cobalt chloride and (c) 3.16 molecular equiv
alents of diethylcadmium, whereby solid non-sticky poly
butadiene having a ratio of 1,2-addition units in excess
of 70% is formed.
14. The catalytic polymerization of 1,3~butadiene com
prising contacting said butadiene with a catalyst in the
presence of an aliphatic hydrocarbon as solvent at a tem
perature between —40° and +40° C. and at a pressure
of at most 5 atmospheres, said catalyst consisting essen
UNITED STATES PATENTS
2,832,759
Nowlin et al. ________ __ Apr. 29, 1958
2,905,659
2,920,062,
2,977,349
Miller _____________ __ Sept. 22, 1959
McFarland ___________ __ Jan. 5, 1960
Brockway- __________ __ Mar. 28, 1961
‘
543,292
779,111
789,781
FOREIGN PATENTS
Belgium ____'_ _______ __ June 2, 1956
Great Britain ________ ..._ July 17, 1957
Great Britain _________ __ Jan. 29, 1958
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